CN106745037A - A kind of multi-stage porous titanium si molecular sieves and preparation method thereof - Google Patents
A kind of multi-stage porous titanium si molecular sieves and preparation method thereof Download PDFInfo
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
A kind of preparation method of multi-stage porous titanium si molecular sieves, comprises the following steps：The preparation of S1, xerogel；S2, the sulfuric acid of xerogel are carbonized in advance：Stirred during xerogel is added into sulfuric acid solution, be evaporated solution post processing, obtain solid powder；The high temperature carbonization of S3, xerogel：Solid powder is put into tube furnace, is processed under inert gas shielding, obtain C SiO2‑TiO2Compound；The preparation of S4, multi-stage porous titanium si molecular sieves：By C SiO2‑TiO2Compound, micropore template agent, alkali source and deionized water are well mixed, and multi-stage porous titanium-silicon molecular sieve is obtained after crystallization, washing, drying, roasting.Advantage is：1., using tween, Span, Qula be logical or the compound such as glucan is mesoporous carbon source, synthesis cost is reduced.2. during, multi-stage porous titanium-silicon system with molecular sieve for preparing is standby, xerogel is first carbonized in advance through sulfuric acid, high temperature carbonization treatment again, makes inorganic ti sources and silicon source effectively be wrapped in the Carbon Materials that charing is formed, and effectively solves diffusion limitation of the intrinsic micropore of Ti-Si zeolite to catalytic reaction.
Description
Technical field
The invention belongs to HTS preparing technical field.Relate in particular to a kind of multi-stage porous titanium si molecular sieves and
Its preparation method.
Background technology
HTS (TS-1) is a kind of catalysis material with MFI topological structures, by Taramasso etc. in nineteen eighty-three
Synthesize first.TS-1 is with dilute H2O2For oxidant a series of oxidation operations reaction in, show good catalysis activity and
Selectivity, and it is substantially pollution-free to environment, therefore, causing the extensive concern of domestic and international researcher.But, due to TS-1's
(0.55nm) is more narrow in aperture, and the larger reactant molecule of kinetic diameter can not enter in its duct and activated centre to be occurred
Effect, limits its application in macromolecular reaction.The nineties in last century, the appearance of mesoporous titanium-silicon molecular screen overcame this
Limitation.
The mesoporous titanium-silicon molecular screens such as Ti-MCM-41, Ti-SBA-15, Ti-HMS and Ti-MCM-48 have broad duct
(more than 2nm) and larger specific surface area, can be used for the Selective Oxidation of larger molecular organicses.However, meso titanium silica molecule
The amorphism of sieve aperture wall, significantly constrains its application industrially.Therefore, how by TS-1 and mesoporous titanium-silicon molecular screen
Advantage combine, prepare while having the multi-stage porous titanium-silicon of large specific surface area, good catalytic activity and stability
Molecular sieve, as this area study hotspot in recent years.
At present, the preparation method of the multi-stage porous titanium si molecular sieves reported mainly has two categories below.One is with mesoporous
HTS is main body, is assembled by crystallization of pore wall or nanometer, and the micro- of TS-1 is introduced in mesoporous titanium-silicon molecular screen structure
Hole and construction unit.Trong On etc. (Micropor.Mesopor.Mater., 2001,44-45,435) use crystallization of pore wall
Method, introduces TS-1 zeolite building units in mesoporous molecular sieve structure, and UL-TS-1 is obtained.But the crystalline substance of mesopore molecular sieve hole wall
Changing may even cave in along with the distortion of meso-hole structure.Nanoclusters self-assembly synthesizes with zeolite primary and secondary structure first
The nano-cluster of unit, then recycles these nano-clusters and mesoporous Micellar Gel self assembly, prepares with hydrothermally stable higher
Mesoporous titanium-silicon molecular screen (the J.Am.Chem.Soc.2002,124,888 of property；Micropor.Mesopor.Mater.,2004,
72,193；Chem.Mater.,2007,19,1664).But, nanoclusters self-assembly preparation process is complicated, condition is harsh.
The second is based on TS-1 zeolite molecular sieve crystals, by post processing or template, in TS-1 zeolite molecular sieves
Larger hole is createed in crystal.Post treatment method is formed by acid, alkali or vapor removal zeolitic frameworks atom in zeolite crystal
Cavitation damage and then the larger hole of generation, can improve the scattering nature of zeolite.But, zeolite molecular sieve crystallinity after treatment
Decline, activated centre is likely to be broken, and the amount of zeolite molecular sieve also has loss.Template used by template includes rigid hard
The soft template of template and flexibility.It is soft template that researcher uses some surfactants containing methoxy silane end group, is prepared
Multi-stage porous titanium si molecular sieves (J.Catal., 2010,269,161；Fuel,2014,130,70；Appl.Catal.A:Gen.,
2012,435,32；Chem.Eng.J.,2011,171,1428).But, these surfactants are general costly, and prepare
Technics comparing is complicated.Researcher uses different Carbon Materials to introduce mesopore orbit in the skeleton of TS-1 for hard template
(Chem.Commun.,2000,2157；Catal.Commun.,2007,8,817；Chem.Commun.,2011,47,3529；
Micropor.Mesopor.Mater.,2011,142,494).But, these Carbon Materials it is general be not easy to be evenly dispersed into it is whole
In individual synthetic system, it is weaker with active force between inorganic precursor species, is unfavorable for the performance of its template action.
The content of the invention
In order to solve above-mentioned technological deficiency, the present invention provides Jie for being provided simultaneously with TS-1 zeolite micropores duct and integrated distribution
A kind of multi-stage porous titanium si molecular sieves in hole duct and preparation method thereof.
One aspect of the present invention protects a kind of preparation method of multi-stage porous titanium si molecular sieves, comprises the following steps：
The preparation of S1, xerogel：
Under stirring, silicon source, titanium source, 0.05mol/L hydrochloric acid, mesoporous carbon source and deionized water are well mixed, so
Alkali source plastic is added with the amount that the molar ratio of mesoporous carbon source is 0.01~2 according to alkali source afterwards, will be obtained after gel drying, grinding
Acid system xerogel；
Or
Prepare alkaline system xerogel：Under stirring, by silicon source, titanium source, micropore template agent, alkali source and deionized water
It is well mixed, steam alcohol；Molar ratio according to mesoporous carbon source and silicon source is 0.01~2 amount mesoporous carbon source aqueous solution of addition, will
The mesoporous carbon source aqueous solution prepared is added to be well mixed in above-mentioned solution and obtains colloidal sol, dries, alkali is obtained after grinding colloidal sol
Gonosome system xerogel；
S2, the sulfuric acid of xerogel are carbonized in advance：Xerogel prepared by step S1 is added to the sulfuric acid that concentration is 1~30% molten
1~24h is stirred in liquid, after being evaporated solution, 4~72h is processed at 120~200 DEG C, obtain solid powder；
The high temperature carbonization of S3, xerogel：The solid powder that step S2 is prepared is put into tube furnace constant temperature zone, lazy
Property gas shield under, at 400~1000 DEG C process 1~60h, obtain C-SiO2-TiO2Compound；
The preparation of S4, multi-stage porous titanium si molecular sieves：By C-SiO2-TiO2Compound, micropore template agent, alkali source and go from
Sub- water is well mixed, then is transferred in autoclave, and multi-stage porous titanium si molecular sieves are obtained after crystallization, washing, drying, roasting.
Second aspect present invention, the multi-stage porous titanium si molecular sieves that the protection above method is prepared.
A kind of multi-stage porous titanium si molecular sieves and preparation method thereof, its advantage is：
1., using cheap tween, Span, Qula be logical or the series compound such as glucan is mesoporous carbon source, substantially reduce
The synthesis cost of molecular sieve.
2. during, multi-stage porous titanium-silicon system with molecular sieve for preparing is standby, xerogel is first carbonized in advance through sulfuric acid, then through high temperature carbonization at
Reason, can be such that inorganic ti sources and silicon source species are effectively wrapped in the Carbon Materials that charing is formed, and then in conventional microporous titanium silicon point
Generate that pore-size distribution more concentrates in sub- sieve skeleton frame is mesoporous, efficiently solves the intrinsic micropore of Ti-Si zeolite to catalytic reaction
Diffusion limitation；Meanwhile, shown than tradition in catalytic oxidation of hydrogen peroxide reaction especially bulky molecular catalysis oxidation reaction
The more preferable catalytic performance of HTS.
3., the inventive method prepare multi-stage porous titanium si molecular sieves can as catalyst, catalyst carrier and adsorbent,
It is primarily adapted for use in petrochemical industry and field of fine chemical.
Brief description of the drawings
Fig. 1 is the X-ray of the embodiment of the present invention one, embodiment two, embodiment six and the multistage pore canal TS-l of comparative example one
Diffraction spectrogram；
In figure, embodiment six, embodiment two, embodiment one, the x-ray diffraction pattern of comparative example one are followed successively by from top to bottom；
Fig. 2 is the nitrogen adsorption-desorption isotherm linear graph of the multistage pore canal TS-l of embodiment one；
Fig. 3 is the BJH pore size distribution figures of embodiment one.
Specific embodiment
One aspect of the present invention protects a kind of preparation method of multi-stage porous titanium si molecular sieves, comprises the following steps：
The preparation of S1, xerogel：
Under stirring, silicon source, titanium source, 0.05mol/L hydrochloric acid, mesoporous carbon source and deionized water are well mixed, so
Alkali source plastic is added with the amount that the molar ratio of mesoporous carbon source is 0.01~2 according to alkali source afterwards, will be obtained after gel drying, grinding
Acid system xerogel；
Or
Prepare alkaline system xerogel：Under stirring, by silicon source, titanium source, micropore template agent, alkali source and deionized water
It is well mixed, steam alcohol；Molar ratio according to mesoporous carbon source and silicon source is 0.01~2 amount mesoporous carbon source aqueous solution of addition, will
The mesoporous carbon source aqueous solution prepared is added to be well mixed in above-mentioned solution and obtains colloidal sol, dries, alkali is obtained after grinding colloidal sol
Gonosome system xerogel；
Preferably, in step S1, when preparing acid system xerogel, silicon source：Titanium source：Hydrogen chloride：Mesoporous carbon source：Deionization
Water is according to 1:0.01~0.033:0.004:0.01~2:15~100 molar ratio；
When preparing alkaline system xerogel, silicon source：Titanium source：Micropore template agent：Alkali source：Deionized water is according to 1:0.01~
0.033:0.1~0.6:0.1~2:15~100 molar ratio；
Preferably, in step S1, the temperature for steaming alcohol is 60~80 DEG C.
Preferably, in step S1, silicon source is in Ludox, Silica hydrogel, the positive esters of silicon acis of tetramethyl, tetraethyl orthosilicate ester
It is a kind of.
Preferably, in step S1, titanium source is titanium compound that is water-soluble or being hydrolyzed in water；
Further, the compound is TiCl3、TiCl4, butyl titanate, metatitanic acid tetra isopropyl ester, tetraethyl titanate,
One kind in tetramethoxy titanate ester.
Preferably, in step S1, mesoporous carbon source is TWEEN Series surfactant, the logical series of surfactants of Qula, department
Class's (disk) series of surfactants, glucan series compound or the water soluble compound containing oxygen atom；
Further, the water soluble compound containing oxygen atom is glucose, starch, sucrose, xylan or solubility
Lignin.
S2, the sulfuric acid of xerogel are carbonized in advance：Xerogel prepared by step S1 is added to the sulfuric acid that concentration is 1~30% molten
1~24h is stirred in liquid, after being evaporated solution, 4~72h is processed at a temperature of 120~200 DEG C, obtain solid powder.
Further, in step S2, the liquid-solid ratio of xerogel and sulfuric acid solution is 5~80mL/g；
Preferably, the liquid-solid ratio of xerogel and sulfuric acid solution is 8~20mL/g.
Preferably, in step S2, pre- carbonization temperature is preferably 140~170 DEG C
Preferably, in step S2, sulfuric acid solution concentration is preferably 2~15%.
The high temperature carbonization of S3, xerogel：The solid powder that step S2 is prepared is put into tube furnace constant temperature zone, lazy
Property gas shield under, at a temperature of 400~1000 DEG C process 1~60h, obtain C-SiO2-TiO2Compound.
Preferably, in step S3, inert gas is pure nitrogen gas or argon gas etc.；Preferably pure nitrogen gas；
Preferably, in step S3, high temperature carbonization treatment is carried out in tube-type atmosphere furnace；
The preparation of S4, multi-stage porous titanium si molecular sieves：By C-SiO2-TiO2Compound, micropore template agent, alkali source and go from
Sub- water is well mixed, then is transferred in autoclave, and multi-stage porous titanium si molecular sieves are obtained after crystallization, washing, drying, roasting.
Preferably, in step S4, C-SiO2-TiO2Compound, micropore template agent, alkali source and deionized water are according to 1:0.1~
1.0:0.1~2:10~100 mixed in molar ratio is uniform, and C-SiO in proportioning2-TiO2Contained SiO in compound2Mole
As described C-SiO2-TiO2The mole of compound.
Preferably, in step S1, S4, micropore template agent is TMAH, tetraethyl ammonium hydroxide, tetrapropyl hydrogen
In amine-oxides, TBAH, 4 bromide, tetraethylammonium bromide, 4-propyl bromide, TBAB
It is a kind of.
Preferably, in step S1, S4, alkali source is TMAH, tetraethyl ammonium hydroxide, tetrapropyl hydroxide
One kind in ammonium, TBAH, ammoniacal liquor, methylamine, dimethylamine, trimethylamine, ethamine, n-propylamine or n-butylamine.
Preferably, in step S4,4~36h is stirred at room temperature；
Preferably, in step S4, it is transferred in the autoclave with PTFE linings；
Preferably, in step S4, in 120~200 DEG C of 8~168h of crystallization.
Second aspect present invention, the multi-stage porous titanium si molecular sieves that the protection above method is prepared.
With regard to embodiment, the invention will be further described below：
Embodiment one
The preparation of S1, xerogel：33.3g tetraethyl orthosilicates are taken in 11.5g hydrochloric acid (0.05mol/L), is stirred at room temperature
2.5h, obtains solution A；1.8g butyl titanates are taken again to be dissolved in 10.5g isopropanols, are slowly dropped into solution A after being well mixed,
Continue to stir 2h, obtain solution B；Take 16.4g polysorbate40s to be dissolved in 35g deionized waters, insert in solution B, continue to stir 3h, obtain
Obtain solution C；
Then, to 2.2g TPAOHs solution (20%) are added in solution C, lurid gel is obtained, will be obtained
The gels overnight for obtaining is dried, and xerogel is obtained after grinding.
S2, the sulfuric acid of xerogel are carbonized in advance：The xerogel for taking 10g steps S1 preparations inserts the sulfuric acid that 150mL concentration is 5%
In solution, 12h is stirred at room temperature, be subsequently placed in dried overnight in baking oven, finally process 24h at 180 DEG C, obtain black and consolidate
Body；
The high temperature carbonization of S3, xerogel：The black solid that step S2 is prepared is put into tube furnace, in purity nitrogen gas bar
(200mL/min) obtains C-SiO by room temperature to 600 DEG C of charing 24h under part2-TiO2Compound；
The preparation of S4, multi-stage porous titanium si molecular sieves：Take 5gC-SiO2-TiO2It is 20% that compound is scattered in 33.8g concentration
TPAOH solution in, 4h is stirred at room temperature, be then transferred to autoclave, the crystallization 48h under the conditions of 175 DEG C；By institute
After the solid washing, filtering, the drying that obtain, it is calcined 8h in 550 DEG C and obtains multistage pore canal TS-1.
Embodiment two
The preparation of S1, xerogel：Take 33.3g tetraethyl orthosilicates, 1.8g butyl titanates to be dissolved in 18g isopropanols, obtain A
Solution；The TPAOH solution that 40.7g concentration is 20% is taken again to be slowly dropped into solution A, continues to stir 2h, at 80 DEG C
Alcohol 3h is steamed, B solution is obtained；Take 5.1g Dextran 200s 00 to be dissolved in 15g deionized waters, insert in B solution, continue to stir 2h, obtain
Obtain C solution；
Then, it is evaporated under the conditions of 80 DEG C, obtains the gel of brown, gels overnight is dried, xerogel is obtained after grinding；
S2, the sulfuric acid of xerogel are carbonized in advance：The xerogel for taking 10g steps S1 preparations inserts the sulfuric acid that 150mL concentration is 5%
In solution, 12h is stirred at room temperature, be subsequently placed in dried overnight in baking oven, finally process 24h at 180 DEG C, obtain black and consolidate
Body；
The high temperature carbonization of S3, xerogel：The black solid that step S2 is prepared is put into tube furnace, in purity nitrogen gas bar
(200mL/min) obtains C-SiO by room temperature to 600 DEG C of charing 24h under part2-TiO2Compound；
The preparation of S4, multi-stage porous titanium si molecular sieves：Take 5gC-SiO2-TiO2It is 20% that compound is scattered in 33.8g concentration
TPAOH solution in, 4h is stirred at room temperature, be then transferred to autoclave, the crystallization 48h under the conditions of 175 DEG C；By institute
After the solid washing, filtering, the drying that obtain, it is calcined 8h in 550 DEG C and obtains multistage pore canal TS-1.
Embodiment three
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is mesoporous carbon source to tell
Temperature 20, and the mol ratio of polysorbas20/tetraethyl orthosilicate is 0.08.
Example IV
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is mesoporous carbon source to tell
Temperature 60, and the mol ratio of polysorbate60/tetraethyl orthosilicate is 0.08.
Embodiment five
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is that mesoporous carbon source is department
Class 60, and the mol ratio of the tetraethyl orthosilicate of Span 60/ is 0.08.
Embodiment six
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is that mesoporous carbon source is song
Logical X-100 is drawn, and the mol ratio of triton x-100/tetraethyl orthosilicate is 0.08.
Embodiment seven
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is that mesoporous carbon source is sugarcane
Sugar, and the mol ratio of sucrose/tetraethyl orthosilicate is 0.08.
Embodiment eight
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is that mesoporous carbon source is Portugal
Glycan 10000, and the mol ratio of the tetraethyl orthosilicate of glucan 10000/ is 0.08.
Embodiment nine
The present embodiment prepares multi-stage porous titanium si molecular sieves according to embodiment 1, and difference is that mesoporous carbon source is Portugal
Glycan 40000, and the mol ratio of the tetraethyl orthosilicate of Gentran 40 000/ is 0.08.
Comparative example one
This comparative example prepares TS-1 zeolites according to embodiment 1, and difference is the omission pre- charcoal of sulfuric acid in preparation process
The step of change.
Comparative example two
This comparative example prepares TS-1 zeolites according to embodiment 1, and difference is not use mesoporous carbon in preparation process
Source, and sulfuric acid charing and high temperature carbonization in advance are not carried out.
Embodiment ten
This example demonstrates that the effect of the inventive method gained multi-stage porous titanium molecular sieve catalysis epoxidation of styrene reaction
Really.
Take the 50ml that 10mL methyl alcohol, 1.12mL styrene, 1.5mL hydrogen peroxide (30%) are added sequentially to be connected with condenser pipe
In there-necked flask, be subsequently adding prepared molecular sieve catalyst in embodiment or comparative example, constant temperature oil bath temperature control at 70 DEG C, electricity
Magnetic stirs 3h.Product is constituted by Shanghai Techcomp Instrument Ltd. GC 7890F types gas chromatograph (SE-54 capillaries
Post, 15m × 0.25mm) analysis, toluene is internal standard, and reaction result see the table below 1：
Pore structure parameter and the epoxidation of styrene activity of the molecular sieve that each embodiment of table 1 is prepared with comparative example
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of multi-stage porous titanium si molecular sieves, it is characterised in that：Comprise the following steps：
The preparation of S1, xerogel：
Prepare acid system xerogel：Under stirring, by silicon source, titanium source, 0.05mol/L hydrochloric acid, mesoporous carbon source and go from
Sub- water is well mixed, and then alkali source plastic is added with the amount that the molar ratio of mesoporous carbon source is 0.01~2 according to alkali source, by gel
Acid system xerogel is obtained after dry, grinding；
Or
Prepare alkaline system xerogel：Under stirring, silicon source, titanium source, micropore template agent, alkali source and deionized water are mixed
Uniformly, alcohol is steamed；Molar ratio according to mesoporous carbon source and silicon source is 0.01~2 amount mesoporous carbon source aqueous solution of addition, will be prepared
The mesoporous carbon source aqueous solution be added to be well mixed in above-mentioned solution and obtain colloidal sol, colloidal sol is dried, alkalescence body is obtained after grinding
It is xerogel；
S2, the sulfuric acid of xerogel are carbonized in advance：Xerogel prepared by step S1 is stirred in adding the sulfuric acid solution that concentration is 1~30%
1~24h is mixed, is evaporated, 4~72h is processed at 120~200 DEG C, obtain solid powder；
The high temperature carbonization of S3, xerogel：The solid powder that step S2 is prepared is put into tube furnace constant temperature zone, in indifferent gas
Under body protection, in 1~60h is processed at 400~1000 DEG C, C-SiO is obtained2-TiO2Compound；
The preparation of S4, multi-stage porous titanium si molecular sieves：By C-SiO2-TiO2Compound, micropore template agent, alkali source and deionized water
It is well mixed, then be transferred in autoclave, multi-stage porous titanium si molecular sieves are obtained after crystallization, washing, drying, roasting.
2. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：In step S1,
When preparing acid system xerogel, silicon source：Titanium source：Hydrogen chloride：Mesoporous carbon source：Deionized water is according to 1:0.01~0.033:
0.004:0.01~2:15~100 molar ratio；
When preparing alkaline system xerogel, silicon source：Titanium source：Micropore template agent：Alkali source：Deionized water is 1:0.01~0.033:
0.1~0.6:0.1~2:15~100 molar ratio；
In step S4, C-SiO2-TiO2Compound, micropore template agent, alkali source and deionized water are according to 1:0.1~1.0:0.1~2:
10~100 mixed in molar ratio is uniform, and C-SiO in proportioning2-TiO2Contained SiO in compound2Mole be the C-
SiO2-TiO2The mole of compound.
3. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：Silicon source is that silicon is molten
One kind in the positive esters of silicon acis of glue, Silica hydrogel, tetramethyl, tetraethyl orthosilicate ester.
4. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：In step S1,
Titanium source is titanium compound that is water-soluble or being hydrolyzed in water.
5. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：Step S1, S4
In, micropore template agent is TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, four
One kind in methyl bromide ammonium, tetraethylammonium bromide, 4-propyl bromide, TBAB.
6. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：In step S1,
Mesoporous carbon source is TWEEN Series surfactant, Qula logical series of surfactants, Span series surfactant, glucan system
Row compound or the water soluble compound containing oxygen atom.
7. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：Step S1, S4
In, alkali source is TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, ammoniacal liquor, first
One kind in amine, dimethylamine, trimethylamine, ethamine, n-propylamine or n-butylamine.
8. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：In step S2,
The liquid-solid ratio of xerogel and sulfuric acid solution is 5~80mL/g.
9. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1, it is characterised in that：In step S4,
4~36h is stirred at room temperature；In 120~200 DEG C of 8~168h of crystallization.
10. the multi-stage porous titanium si molecular sieves for being prepared with such as any methods described of claim 1 to 9.
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| CN109336130A (en) * | 2018-10-26 | 2019-02-15 | 天津大学 | Hierarchical pore MTT structure molecular sieve prepared by glucan regulation and control, preparation method and application |
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| CN113353951A (en) * | 2021-07-21 | 2021-09-07 | 中国石油大学(北京) | Hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof |
| CN116040647A (en) * | 2022-12-21 | 2023-05-02 | 中触媒新材料股份有限公司 | Method for synthesizing TS-1 by taking tetramethoxysilane as raw material and application |
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| CN109336130B (en) * | 2018-10-26 | 2021-07-13 | 天津大学 | Hierarchical pore MTT structure molecular sieve prepared by glucan regulation and control, preparation method and application |
| CN112624138A (en) * | 2020-12-19 | 2021-04-09 | 宁波四明化工有限公司 | Preparation method of durable and stable titanium silicalite molecular sieve catalyst for producing 2-nitropropane |
| CN113353951A (en) * | 2021-07-21 | 2021-09-07 | 中国石油大学(北京) | Hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof |
| CN116040647A (en) * | 2022-12-21 | 2023-05-02 | 中触媒新材料股份有限公司 | Method for synthesizing TS-1 by taking tetramethoxysilane as raw material and application |
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